Fluorine-containing ethylene copolymers

ABSTRACT

The present invention is a fluorine containing ethylene copolymer obtained by the copolymerization of ethylene with suitable fluorine-containing comonomer compounds, wherein the fluorine-containing comonomer compound is present at a concentration of up to 40% by weight, based on the total weight of the ethylene copolymer.

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/273,912, filed Mar. 7, 2001.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to ethylene copolymers. Thisinvention particularly relates to fluorine-containing ethylenecopolymers and products made therefrom.

[0004]2. Description of the Related Art

[0005] Fluoropolymer compositions are widely used for surfacemodification, as agents to impart desirable surface properties tovarious types of surfaces. For example, fluoropolymer compositions canimpart or enhance the water and oil repellency of certain surfaces,including fabrics and upholstery. However, surface treatment usingfluoropolymers can involve complex processing steps to ensure that thefluoropolymer is applied and bonded to the surface being treated. Theprocess can be difficult and expensive. Organic solvent vapors can bereleased to the atmosphere during the processing. Surface treatment caninvolve high temperature curing of the fluoropolymer to the substratesurface.

[0006] To impart water and oil repellency, fluorochemicals orfluoropolymers can be dissolved or dispersed either in organic solventsor in water. For example, mixtures of fluorinated copolymers, mainlycomprising perfluoroalkyl methacrylate, and vinyl copolymers aredisclosed in U.S. Pat. No. 3,277,039. U.S. Pat. No. 2,803,615 disclosesacrylate/methacrylate esters of N-alkyl or N-alkanolperfluoroalkanesulfonamides used to impart grease and oil repellency.Fluorochemical compositions for treating textile fibers and fabricscomprising an aqueous solution or dispersion of a fluorochemicalacrylate and a polyalkoxylated polyurethane having pendantperfluoroalkyl groups is described in U.S. Pat. No. 5,350,557. U.S. Pat.No. 5,536,304 describes a composition for imparting water and oilrepellency comprising a fluoroaliphatic radical containing agent, and acyclic carboxylic acid anhydride-containing polysiloxane.

[0007] Fluorochemicals can be melt-blended with thermoplastic polymers,and thereby impart water and oil repellency to the polymer by migratingto the polymer surface as described in, for example, U.S. Pat. No.5,025,052, wherein the preparation of fluoroaliphatic radical-containingoxazolidinone compositions for blending with thermoplastic polymers isdescribed. U.S. Pat. No. 5,380,778 describes thermoplastic compositionscomprising fluoroaliphatic radical containing aminoalcohols and athermoplastic synthetic organic polymer.

[0008] Ethylene copolymers are useful polymeric materials in manyapplications. Ethylene copolymers can find use in applications such aspackaging, laminate films, and adhesives for example. Conventionalpolyolefins such as polypropylene, polyethylene, and conventionalethylene copolymers have high surface tension relative to fluoropolymerssuch as polytetrafluoroethylene, for example. As a result, forapplications wherein water and oil repellency is important, articlesmade from polyolefins must be treated to attain a satisfactory level ofrepellency. However, due to their relatively low melting point and lackof reactive functional groups, treatment of polyolefins withfluorochemicals or fluoropolymers is, in general, much more difficultthan treating other thermoplastic polymers.

[0009] Copolymers of ethylene and fluorine-containing monomers areknown. For example, Tefzel®, manufactured by E.I DuPont de Nemours andCompany, is a copolymer of ethylene and tetrafluoroethylene. Copolymersof this type are very different from conventional polyethylenecopolymers in many aspects. For example, fluorine-containing ethylenecopolymers are typically melt-processable only at much highertemperature than conventional ethylene polymers and ethylene copolymers,and the properties of fluorine-containing ethylene copolymers differform conventional ethylene copolymers. Copolymers of this type are notamenable to manufacture or processing under the type of conditions usedto manufacture and process conventional ethylene copolymers.Ethylene/fluoromonomer copolymers of this type are not compatible insystems that currently use polyethylene copolymers. For example, knownconventional ethylene/tetrafluoroethylene copolymers have no adhesion topolyethylene.

[0010] It would be desirable to have a fluorine-containing ethylenecopolymer that can be processed in the same way as conventional ethylenecopolymers.

[0011] It would be desirable to have a melt-processablefluorine-containing ethylene copolymer.

[0012] It would be desirable to have a fluorine-containing ethylenecopolymer that has a low surface tension.

[0013] It would be desirable to have a fluorine-containing ethylenecopolymer that can be compatible with, or used in place of conventionalethylene copolymers.

[0014] It would be desirable to have a laminate film having at least onelayer of a fluorine-containing ethylene copolymer.

[0015] It would be desirable to have at least a composite fiber havingat least one component of a fluorine-containing ethylene copolymer.

SUMMARY OF THE INVENTION

[0016] In one aspect the present invention is a fluorine containingethylene copolymer obtained by the copolymerization of ethylene withsuitable fluorine-containing comonomer compounds, comprising: from about0.5 wt % to about 40 wt % of a fluorine-containing comonomer compoundand from about 30 wt % to about 99.5 wt % ethylene.

[0017] In another aspect the present invention is a melt-processableethylene copolymer blend comprising a fluorine containing ethylenecopolymer obtained by the copolymerization of ethylene with suitablefluorine-containing comonomer compounds, wherein the fluorine-containingcomonomer compound is present at a concentration of up to 40% by weight,based on the total weight of the ethylene copolymer, and wherein theblend comprises from about 5 to about 95%, by weight,fluorine-containing ethylene copolymer based on the total weight of theblend.

[0018] In another aspect the present invention is an article ofmanufacture, including a molded part, a blown film, a woven or anon-woven fiber, or a multilayer composite film, comprising a fluorinecontaining ethylene copolymer obtained by the copolymerization ofethylene with at least one suitable fluorine-containing comonomercompound, wherein the fluorine-containing comonomer compound is presentat a concentration of up to 40% by weight, based on the total weight ofthe ethylene copolymer.

DETAILED DESCRIPTION OF THE INVENTION

[0019] In one embodiment, the present invention is a fluorine-containingethylene copolymer. Ethylene copolymers of the present invention includeup to about 40% by weight, based on the total weight of the copolymer(wt %), of a suitable fluorine-containing monomer. Preferably thefluorine-containing comonomer is from about 2 to about 30 wt % of thecopolymer. More preferably, the fluorine-containing comonomer is fromabout 10 to about 25 wt % of the copolymer.

[0020] The copolymer comprises from about 30 wt % to about 99.5 wt %ethylene comonomer. Preferably the copolymer comprises from about 40 wt% to about 95 wt % ethylene comonomer, more preferably from about 50 wt% to about 90 wt % ethylene comonomer, and most preferably from about 70wt % to about 90 wt % ethylene comonomer.

[0021] The copolymer can optionally comprise other comonomers. Acopolymer, as the term is used herein, is a polymer obtained by thepolymerization of at least two comonomers. A comonomer, as the term isused herein, is any monomer that is polymerized in the presence of atleast one other monomer to produce a copolymer of the present invention.For example, a copolymer can be the product of polymerization of two,three, four, or five comonomers, or more. Where the concentration of allbut one of the comonomers is specified, the concentration of theremaining comonomer can be deduced by subtraction of the knownconstituents from 100 wt %, that is, the total wt % of the copolymer.

[0022] Suitable fluorine containing comonomers are described in U.S.Pat. No. 2,803,615; U.S. Pat. No. 2,642,416; U.S. Pat. No. 2,826,564;U.S. Pat. No. 3,102,103; U.S. Pat. No. 3,282,905; and U.S. Pat. No.3,304,278, for example. Suitable fluorine-containing comonomers arefluorinated acrylate or methacrylate esters of the general formula:Cf-L-O—CO—CR═CH₂, wherein:

[0023] (i) Cf is a fluorinated aliphatic group having at least 4 carbonatoms wherein the aliphatic group can be: straight chain or branched;acyclic or cyclic; and can include heteroatoms such as nitrogen, oxygen,and/or sulfur. It is preferable that Cf is a perfluorinated aliphaticgroup of the formula C_(n), F_(2n+1), wherein n is an integer from 3 to20;

[0024] (ii) L is a linking group that connects the fluorinated aliphaticgroup with the (meth)acrylate group, wherein L can contain from 1 to 10carbon atoms, and can optionally include oxygen, nitrogen, orsulfur-containing groups, or combinations thereof; L can bestraight-chain or branched, cyclic alkylene, arylene, arylalkylene,sulfonyl, sulfoxy, sulfonamide, carboxyamino, carbonyloxy, urethanylene,or combinations thereof.

[0025] For example, a fluorine-containing monomer suitable for use inthe present invention can include:

[0026] CF₃—(CF₂)_(n)—CH₂—CH₂—O—CO—CH═CH₂;

[0027] CF₃—(CF₂)_(n)—CH₂—CH₂—O—CO—C (CH₃)═CH₂;

[0028] CF₃—(CF₂)₃—CH₂—O—CO—CH═CH₂;

[0029] CF₃—(CF₂)₃—CH₂—O—CO—C (CH₃)═CH₂;

[0030] CF₃—(CF₂)₅—CH₂—O—CO—CH═CH₂;

[0031] (CF₃)₂—CF—(CF₂)₅—CH₂CH₂—O—CO—CH═CH₂;

[0032] CF₃—(CF₂)₇—SO₂N(CH₃)—CH₂—CH₂—O—CO—CH═CH₂;

[0033] CF₃—(CF₂)₇—SO₂N(CH₂CH₃)—CH₂—CH (CH₃)—O—CO—CH═CH₂;

[0034] CF₃—(CF₂)₅—SO₂N(CH₃)—CH₂—CH₂—O—CO—CH═CH₂; and

[0035] (CF₃)₂—CF(CF₂)₄—SO₂N(CH₃)—CH₂—CH₂—O—CO—CH═CH₂,

[0036] wherein n is an integer from 3 to about 20. Mixtures or physicalcombinations of comonomers described by the general formulas above arecontemplated to be within the scope of the present invention.Furthermore, non-acrylic fluoroalkyl monomers can be used in thepractice of the present invention, particularly when using transitionmetal catalysts.

[0037] Copolymers of the present invention can be prepared byconventional methods for polymerization or copolymerization ofpolyethylene polymers and copolymers. For example, copolymers of thepresent invention can be prepared by copolymerization of ethylene withfluorine containing comonomers described herein by high pressure freeradical polymerization or, alternatively, by using low pressuretransition metal catalysis. Using high pressure free radicalpolymerization is preferred herein. Conventional methods for preparingethylene copolymers are described in patented literature and referencetextbooks. For example, an ethylene copolymerization process isdescribed in U.S. Pat. No. 4,351,931.

[0038] Copolymers of the present invention are melt-processable polymersand can be processed by methods used with conventional ethylenecopolymers. For example, copolymers of the present invention can bemolded, extruded, blown, or spun to yield molded parts, fibers, orfilms, for example, in the same manner as conventional polyethylenepolymers and copolymers.

[0039] Unlike conventional ethylene copolymers, polymers of the presentinvention have low surface tension. Copolymers and copolymer blends ofthe present invention have surface tensions of less than those ofconventional polyethylene and/or polypropylene polymers and copolymers.Copolymers (including blends) of the present invention have surfacetensions of less than about 32 dyne/cm. Preferably, the surface tensionis less than about 28 dyne/cm, and more preferably less than about 24dyne/cm.

[0040] In another embodiment, the present invention is a terpolymercomprising in addition to the above comonomers, from about 0.5 wt % toabout 5 wt % of a terpolymer X, wherein X is a reactive functionalcomonomer. For example, X can be glycidyl methacrylate, maleicanhydride, or a half-ester of maleic anhydride and/or derivativesthereof. Preferably, the terpolymer includes from about 1 wt % to about4.5 wt % of X, more preferably from about 1.5 wt % to about 4 wt % of X.Most preferably the terpolymer comprises from about 2 wt % to about 4 wt% of X.

[0041] In still another embodiment, the present invention is aterpolymer comprising, in addition to the ethylene and fluoroalkylcomonomers described hereinabove, from about 0.5 wt % to about 50 wt %of a terpolymer Y, wherein Y is a vinyl acetate or an acrylatecomonomer, such as methyl acrylate and butyl acrylate. Preferably Y isincluded in an amount of from about 2 wt % to about 45 wt %, and morepreferably from about 5 wt % to about 40 wt %. Most preferably, Y isincluded in an amount of from about 5 wt % to about 35 wt %. PreferablyY is a vinyl acetate monomer.

[0042] In another embodiment, the present invention is a terpolymercomprising, in addition to the ethylene and fluoroalkyl comonomersdescribed hereinabove, from about 1.0 to about 20 wt % of a terpolymerZ, wherein Z is acrylic acid or methacrylic acid comonomer. Preferably Zis included in an amount of from about 1.5 wt % to about 18 wt %, andmore preferably from about 2.5 wt % to about 17 wt %. Most preferably Zis included in an amount of from about 3 wt % to about 15 wt %.

[0043] In still another embodiment, the present invention is afluorine-containing ethylene copolymer comprising, in addition to atleast 40 wt % ethylene and from 0.5 wt % to about 40 wt % fluoroalkylcomonomer, any combination of at least two comonomers selected from thegroup consisting of X, Y, and Z in a total amount of from about 0.5 wt %to about 59.5 wt %. Preferably the two comonomers are present in a totalamount of from about 2 wt % to about 50 wt %, more preferably in anamount of from about 5 wt % to about 45 wt %, and most preferably in anamount of from about 7 wt % to about 40 wt %. Preferably the combinationincludes Y.

[0044] In another embodiment, the present invention is a composite filmthat includes at least one layer of an ethylene/fluoroalkyl copolymer ofthe present invention. A composite film of the present invention can beobtained in the same manner as composite films comprising conventionalpolyethylene polymer or copolymer layers with other polymer layers. Forexample, U.S. Pat. No. 3,589,976 describes a process suitable for makingthe composite films of polystyrene polyolefins made by a coextrusionprocess. Composite films of the present invention can include laminatecomposite films, with or without adhesive layers.

[0045] In another embodiment, the present invention is a composite fiberthat includes at least one component of an ethylene/fluoroalkylcopolymer of the present invention. A composite fiber of the presentinvention can be obtained in the same manner as composite fiberscomprising conventional polymers. U.S. Pat. No. 3,329,557 describes apreparation of composite fibers of nylon and poly(ethylene terephalate)for making antistatic filaments.

[0046] Copolymers of the present invention can be used alone or inblends with other polymers, for example, thermoplastic materials andthermoplastic elastomers. Polymers suitable for blending with copolymersof the present invention include, for example: polyamides, polyethyleneterephthalate, polyurethane, polystyrene, polyethylene, ethylenecopolymers, and polypropylene. Blends of the present invention includefrom about 1 wt % to about 99 wt % of the fluorine containing ethylenecopolymer of the present invention. Preferably blends of the presentinvention comprise from about 5 wt % to about 95 wt % of thefluorine-containing ethylene copolymer, more preferably from about 10 wt% to about 90 wt %, and most preferably from about 20 wt % to about 80wt %. Copolymers can be used in a process for making films or in aprocess for making woven or nonwoven fibers, for example.

EXAMPLES

[0047] The following examples are merely illustrations of the presentinvention, and not intended to limit the scope of the present inventionin any way.

[0048] Testing

[0049] Melt Index (MI) was measured using ASTM D1238 using a 2160 gramweight, and measured at 190° C. Melting Point was measured usingDifferential Scanning Calorimetry (DSC), using a DuPont Thermalanalyzer.

[0050] Surface tension (surface energy) was measured on blown films ofthe Examples and the Comparison Examples using a Video Contact AngleSystem instrument, for AST PRODUCT, Inc. The film samples of 3-4 milwere made from a laboratory blown film equipment. Surface tension wascalculated base on the Harmonic-Mean Method as described in PolymerInterface and Adhesion, Sougeng Wu, Marcel Dekker, Inc., 1982. Deionizedwater having a surface tension of 71.8 dynes/cm and methylene iodidehaving a surface tension of 50.8 dynes/cm were used in the contact anglemeasurements.

[0051] Analysis of fluorine content was by Ion Chromatography (IC). Thesamples were combusted in oxygen-filled sealed flasks. The combustiongases were collected in a weakly basic catch solution. The catchsolution was taken to a known volume and analyzed by IC.

[0052] Compositions of ethylene/perfluoroalkyl (meth)acrylate copolymerswere measured and calculated by fluorine content alone. Compositionsthat include vinyl acetate and methyl acrylate were measured by acombination of fluorine content analysis and infrared spectroscopy (IR).

[0053] Ethylene copolymers listed in Table 1 were prepared according tothe following procedures. Ethylene was copolymerized in the presence offluoroalkyl(meth)acrylate monomers. The free radical polymerizationswere carried out at high pressure (27,000 psi) and a temperaturesranging from 160° C. to 250° C., in the presence of a peroxide freeradical initiator.

[0054] Example C1 is not an example of the present invention, and is acopolymer of ethylene and methacrylic acid, prepared under the sameconditions as the examples of the present invention.

[0055] Example 1 is a terpolymer of ethylene, methacrylic acid, andZonyl® TA-N

[0056] Examples 2-6, Example 9 and Examples 11-19 are copolymers ofethylene and either Zonyl® TA-N or Zonyl® TM.

[0057] Examples 7 and 8 are terpolymers of ethylene, vinyl acetate, andZonyl® TM.

[0058] Example 10 is a terpolymer of ethylene, methyl acrylate andZonyl® TM. It is an amorphous polymer without a melting point.

[0059] The blends of fluorine-containing copolymers, Examples 20-26, arelisted in Table 2. The blends were prepared in a 30 mm twin screwextruder.

[0060] Example C2 is not an example of this invention, and is a lowdensity polyethylene with a MI of 4.4 and a melting point of 115° C.

[0061] Examples 20-21 and Examples 23-24 are blends of LDPE described inC2, and either Zonyl® TM or Zonyl® TA-N.

[0062] Example 22 is a blend of PP and Zonyl® TM. The PP is apolypropylene with a MI of 1.5 and a melting point of 166° C.

[0063] Examples 25-26 are blends of HDPE and Zonyl® TA-N. The HDPE is ahigh-density polyethylene with a MI of 0.6 and a melting point of 139°C.

[0064] Zonyl® TA-N and Zonyl® TM are both available from E. I. DuPont deNemours and Company. Zonyl® TA-N is a perfluoroalkylethyl acrylate ofthe general formula: C_(n)F_(2n+1)CH₂CH₂O(CO)CH═CH₂, wherein n is aninteger from 5 to about 20. Zonyl® TM is a perfluoroalkylethylmethacrylate of the general formula: C_(n)F_(2n+1)CH₂CH₂O(CO)C(CH₃)═CH₂,wherein n is an integer from 3 to about 20. TABLE 1 Examples (Ex.) 1-19Copolymers of Ethylene and Perfluoroalkyl (meth) acrylate SurfacePolymer F Melting Tension ization Composition content MI at Point(dynes/ Temp Ex. (wt %) (wt %) 190° C. (° C.) cm) (° C.) C1 E/MAA 0.0093122 96 34.8 250 (90/10)  1 E/MAA/TAN 0.4 96 96 31.3 250 (89/10/0.6)  2E/TAN 0.38 69 110.4 30.6 250 (99.4/0.6)  3 E/TAN 0.52 29 110 28.63 250(99.2/0.8)  4 E/TM 0.3 82 111 30.1 250 (99.5/0.5)  5 E/TM 0.63 81 11129.5 250 (98.9/1.1)  6 E/TM 1.45 123 110 25.2 250 (97.6/2.4)  7 E/VA/TM1.98 43 72 26.2 210 (71.9/24.5/3.6)  8 E/VA/TM 1.48 37 87 29 210(80/17.2/2.8)  9 E/TM 4.0 144 109 23.1 260 (93.3/6.7) 10 E/MA/TM 1.78 14Amorphous NA 165 (34/62/3) 11 E/TM 3.69 22 117.6 23 210 93.8/6.2) 12E/TM 4.84 28 117.2 22 210 (91.9/8.1) 13 E/TM (93.3/ 4 14 118.3 24.5 1906.7) 14 E/TM (93.7/6.3 3.76 20 114 24.6 230 15 E/TM (93.5/ 3.9 35 11224.2 250 6.5) 16 E/TAN 4.2 16 114.3 24.6 210 (93.4/6.6) 17 E/TAN 4.5 52114 25 210 (92.9/7.1) 18 E/TAN 7.4 80 112.7 22.3 210 (88.4/11.6) 19E/TAN 9.7 110 110 21 210 (84.7/15.3)

[0065] TABLE 2 Surface Properties of Blends of Ethylene/Perfluoroalkyl(meth) acrylate Copolymers Surface Tension Examples Blend Composition(wt. %) (dyne/cm) C2 LDPE 33.6 20 LDPE/Example 9 (80/20) 25.5 21LDPE/Example 9 (60/40) 24.2 22 PP/Example 9 (80/20) 27.0 23 LDPE/Example12 (60/40) 24.1 24 LDPE/Example 13 (60/40) 23.7 25 HDPE/Example 12(60/40) 26.2 26 HDPE/Example 13 (60/40) 24.7

1. A fluorine containing ethylene copolymer obtained by thecopolymerization of ethylene with suitable fluorine-containing comonomercompounds, comprising: from about 0.5 wt % to about 40 wt % of afluorine-containing comonomer compound and from about 30 wt % to about99.5 wt % ethylene.
 2. The copolymer of claim 1 wherein thefluorine-containing comonomers are fluorinated acrylate or methacrylateesters of the general formula: Cf-L-O—COCR═CH₂, wherein: (i) Cf is afluorinated aliphatic group having at least 4 carbon atoms; (ii) L is alinking group that connects the fluorinated aliphatic group with the(meth)acrylate group, wherein L can contain from 1 to 10 carbon atoms;(iii) R is H or CH₃.
 3. The copolymer of claim 2 wherein Cf is aperfluorinated aliphatic group of the general formula: C_(n)F_(2n+1),wherein n is an integer of from 3 to about
 30. 4. The copolymer of claim4 wherein L is a linking group selected from the group consisting of:—CH₂—CH₂—; —CH₂—; —SO₂N(CH₃)—CH₂—CH₂—; and —SO₂N(CH₂CH₃)—CH₂—CH (CH₃)—.5. The copolymer of claim 1 additionally comprising: from about 0.5 toabout 5 wt % of X, wherein X is a reactive functional comonomer.
 6. Thecopolymer of claim 5 wherein X is a comonomer selected from the groupconsisting of: glycidyl methacrylate, maleic anhydride, or a half esterof maleic anhydride.
 7. The copolymer of claim 6 wherein X is maleicanhydride or a half-ester of maleic anhydride.
 8. The copolymer of claim6 wherein X is glycidyl methacrylate.
 9. The copolymer of claim 5comprising: from about 1.0 to about 4.5 wt % of X.
 10. The copolymer ofclaim 9 comprising: from about 1.5 to about 4.0 wt % of X.
 11. Thecopolymer of claim 1 additionally comprising: from about 0.5 to about 50wt % of Y, wherein Y is a vinyl acetate or an acrylate comonomer. 12.The copolymer of claim 11 comprising from about 2 wt % to about 45 wt %of Y.
 13. The copolymer of claim 12 comprising from about 5 wt % toabout 40 wt % Y.
 14. The copolymer of claim 13 comprising from about 5wt % to about 35 wt % Y.
 15. The copolymer of claim 14 wherein Y is avinyl acetate monomer.
 16. The copolymer of claim 1 additionallycomprising: from about 1.0 to about 20 wt % of comonomer Z, wherein Z isacrylic acid or methacrylic acid.
 17. The copolymer of claim 16comprising from about 1.5 wt % to about 18 wt % of comonomer Z.
 18. Thecopolymer of claim 17 comprising from about 2.5 to about 17 wt % Z. 19.The copolymer of claim 18 comprising from about 3 wt % to about 15 wt %Z.
 20. The copolymer of claim 1 additionally comprising: any combinationof at least two comonomers selected from the group consisting of X, Y,and Z wherein the combination is present in a total amount of from about0.5 wt % to about 59.5 wt %, and wherein X is a reactive functionalcomonomer, Y is a vinyl acetate or an acrylate comonomer, and Z is anacrylic acid or methacrylic acid comonomer.
 21. The copolymer of claim20 wherein ethylene is present in an amount of from about 40 wt % toabout 99.5 wt %, and the fluorine-containing comonomer is present in anamount of from about 0.5 wt % to about 40 wt %.
 22. A melt-processableethylene copolymer blend comprising: (A) a fluorine containing ethylenecopolymer obtained by the copolymerization of ethylene with suitablefluorine-containing comonomer compounds, wherein the fluorine-containingcomonomer compound is present at a concentration of up to 40% wt %, andwherein the blend comprises from about 5 to about 95 wt % of thefluorine-containing ethylene copolymer, based on the total weight of theblend; and (B) a second polymer component wherein (B) is present in anamount of from about 5 wt % to about 95 wt % based on the weight of theblend.
 23. The blend of claim 22 wherein (B) is a polyethylene polymer.24. The blend of claim 22 wherein (B) is a polypropylene polymer. 25.The blend of claim 22 wherein (B) is an ethylene copolymer.
 26. Theblend of claim 22 wherein (B) is a thermoplastic polymer orthermoplastic elastomer.
 27. An article of manufacture comprising afluorine containing ethylene copolymer obtained by the copolymerizationof ethylene with suitable fluorine-containing comonomer compounds,comprising: from about 0.5 wt % to about 40 wt % of afluorine-containing comonomer compound and from about 40 wt % to about99.5 wt % ethylene.
 28. The copolymer of claim 1 wherein the copolymeris obtained by a process comprising the step: copolymerizing ethyleneand a fluorine containing comonomer using high-pressure free radicalpolymerization.